Near-infrared-driven upconversion nanoparticles with photocatalysts through water-splitting towards cancer treatment.

Water splitting is promising, especially for energy and environmental applications; however, there are limited studies on the link between water splitting and cancer treatment. Upconversion nanoparticles (UCNPs) can be used to convert near-infrared (NIR) light to ultraviolet (UV) or visible (Vis) light and have great potential for biomedical applications because of their profound penetration ability, theranostic approaches, low self-fluorescence background, reduced damage to biological tissue, and low toxicity. UCNPs with photocatalytic materials can enhance the photocatalytic activities that generate a shorter wavelength to increase the tissue penetration depth in the biological microenvironment under NIR light irradiation. Moreover, UCNPs with a photosensitizer can absorb NIR light and convert it into UV/vis light and emit upconverted photons, which excite the photoinitiator to create H2, O2, and/or OH˙ via water splitting processes when exposed to NIR irradiation. Therefore, combining UCNPs with intensified photocatalytic and photoinitiator materials may be a promising therapeutic approach for cancer treatment. This review provides a novel strategy for explaining the principles and mechanisms of UCNPs and NIR-driven UCNPs with photocatalytic materials through water splitting to achieve therapeutic outcomes for clinical applications. Moreover, the challenges and future perspectives of UCNP-based photocatalytic materials for water splitting for cancer treatment are discussed in this review.

Organic-inorganic hybrid material for hole transport in inverted perovskite solar cells.

Hole mobility is critical to the power conversion efficiencies of perovskite solar cells (PSCs). Organic small-molecule hole-transporting materials (HTMs) have attracted considerable interest in PSCs due to their structural flexibility and operational durability, but they suffer from modest hole mobility. On the other hand, inorganic HTMs with good hole mobility are inflexible in structural variation and exhibit unsatisfactory cell efficiency. In this study, a ligand BT28 and its zinc-based coordination complex BTZ30 were synthesized, characterized, and investigated as HTMs for PSC applications. The mixed-halide perovskites can be grown uniformly with large crystalline grains on both HTMs, which exhibit similar optical and electrochemical properties. However, it was discovered that the BTZ30-based solar cell exhibited an open-circuit voltage of 1.0817 V and a high short-circuit current density of 23.1392 mA cm-2 with a champion power conversion efficiency of close to 20 %. The performance difference between the two HTMs can be attributed to the difference in their hole mobilities, which is 63.31 % higher for BTZ30 than BT28. The comparison of non-metal and metal HTMs revealed the importance of considering hybrid structures to overcome some shortcomings associated with organic and inorganic HTMs and achieve high-performance PSCs.

Heterocyclic Functionalized Donor-Acceptor Hole-Transporting Materials for Inverted Perovskite Solar Cells.

Hole transport materials (HTMs) with appropriate energy levels and comprehensive passivation effects help to obtain highly efficient and stable perovskite solar cells (PSCs). Electron-deficient character-induced HTMs can generate varying energy level alignments near the HTM/perovskite interface. Herein, we report the synthesis and investigation of two new dipolar HTMs, WWC103 and WWC105, based on 2-(1,1-dicyanomethylene)rhodamine and 4-cynophenylacetonitrile acceptors, enabling high-efficiency mixed-cation mixed-halide perovskite solar cells. Apart from having different acceptors, these HTMs are built on a heterocyclic frame, which can provide passivation effects and improve the morphology of the perovskite layer. As a result, these dopant-free HTM-based solar cells show a high open-circuit voltage and good power conversion efficiency. Among both, the solar cell based on the HTM with 2-(1,1-dicyanomethylene)rhodamine exhibits a high open-circuit voltage of 1.09 V with a champion power conversion efficiency of over 20.51%. The improved performance of WWC103 over WWC105 (19.74%) is attributed to the new acceptor, which, in addition to providing good energy-level alignments and hole mobility, also holds the ability to passivate the defects. The findings suggest a new acceptor unit for constructing dopant-free HTMs for efficient PSCs.

Defect Mediated Improvements in the Photoelectrochemical Activity of MoS2/SnS2 Ultrathin Sheets on Si Photocathode for Hydrogen Evolution.

Solar-driven water electrolysis to produce hydrogen is one of the clean energy options for the current energy-related challenges. Si as a photocathode exhibits a large overpotential due to the slow hydrogen evolution reaction (HER) kinetics and hence needs to be modified with a cocatalyst layer. MoS2 is a poor HER cocatalyst due to its inert basal plane. Activation of the MoS2 basal plane will facilitate HER kinetics. In this study, we have incorporated SnS2 into MoS2 ultrathin sheets to induce defect formation and phase transformation. MoS2/SnS2 composite ultrathin sheets with a Sn2+ state create a large number of S vacancies on the basal sites. The optimized defect-rich MoS2/SnS2 ultrathin sheets decorated on surface-modified Si micro pyramids as photocathodes show a current density of -23.8 mA/cm2 at 0 V with an onset potential of 0.23 V under acidic conditions, which is higher than that of the pristine MoS2. The incorporation of SnS2 into 2H-MoS2 ultrathin sheets not only induces a phase but also can alter the local atomic arrangement, which in turn is verified by their magnetic response. The diamagnetic SnS2 phase causes a decrease in symmetry and an increase in magnetic anisotropy of the Mo3+ ions.

MOF-Derived Cu-BTC Nanowire-Embedded 2D Leaf-like Structured ZIF Composite-Based Aptamer Sensors for Real-Time In Vivo Insulin Monitoring.

Insulin, which is a hormone produced by the ß-cells of the pancreas, regulates the glucose levels in the blood and can transport glucose into cells to produce glycogen or triglycerides. Insulin deficiency can lead to hyperglycemia and diabetes. Therefore, insulin detection is critical in clinical diagnosis. In this study, disposable Au electrodes were modified with copper(II) benzene-1,3,5-tricarboxylate (Cu-BTC)/leaf-like zeolitic imidazolate framework (ZIF-L) for insulin detection. The aptamers are easily immobilized on the Cu-BTC/ZIF-L composite by physical adsorption and facilitated the specific interaction between aptamers and insulin. The Cu-BTC/ZIF-L composite-based aptasensor presented a wide linear insulin detection range (0.1 pM to 5 µM) and a low limit of detection of 0.027 pM. In addition, the aptasensor displayed high specificity, good reproducibility and stability, and favorable practicability in human serum samples. For the in vivo tests, Cu-BTC/ZIF-L composite-modified electrodes were implanted in non-diabetic and diabetic mice, and insulin was quantified using electrochemical and enzyme-linked immunosorbent assay methods.

Molybdenum Disulfide/Tin Disulfide Ultrathin Nanosheets as Cathodes for Sodium-Carbon Dioxide Batteries.

Metal-CO2 rechargeable batteries are of great importance due to their higher energy density and carbon capture capability. In particular, Na-CO2 batteries are potential energy-storage devices that can replace Li-based batteries due to their lower cost and abundance. However, because of the slow electrochemical processes owing to the carbonated discharge products, the cell shows a high overpotential. The charge overpotential of the Na-CO2 battery increases because of the cathode catalyst's inability to break down the insulating discharge product Na2CO3, thereby resulting in poor cycle performance. Herein, we develop an ultrathin nanosheet MoS2/SnS2 cathode composite catalyst for Na-CO2 battery application. Insertion of SnS2 reduces the overpotential and improves the cyclic stability compared to pristine MoS2. As shown by a cycle test with a restricted capacity of 500 mAh/g at 50 mA/g, the battery is stable up to 100 discharge-charge cycles as the prepared catalyst successfully decomposes Na2CO3. Furthermore, the battery with the MoS2/SnS2 cathode catalyst has a discharge capacity of 35 889 mAh/g. The reasons for improvements in the cycle performance and overpotential of the MoS2/SnS2 composite cathode catalyst are examined by a combination of Raman, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure analysis, which reveals an underneath phase transformation and changes in the local atomic environment to be responsible. SnS2 incorporation induces S-vacancies in the basal plane and 1T character in 2H MoS2. This combined impact of SnS2 incorporation results in undercoordinated Mo atoms. Such a change in the electronic structure and the phase of the MoS2/SnS2 composite cathode catalyst results in higher catalytic activity and reduces the cell overpotential.

Boosting Solar Hydrogen Production of Molybdenum Tungsten Sulfide-Modified Si Micropyramids by Introducing Phosphate.

Si is regarded as a promising photocathode material for solar hydrogen evolution reaction (HER) because of its small band gap and highly negative conduction band edge. However, bare Si electrodes have high overpotential because of sluggish HER kinetics on the surface. In this study, molybdenum tungsten sulfide (MoS2-WS2) was decorated on Si photocathodes as the co-catalyst to accelerate HER kinetics. The catalytic performance of MoS2-WS2 was further enhanced by introducing phosphate materials. Phosphate-modified molybdenum tungsten sulfide (PO-MoWS) was deposited on Si photoabsorbers to provide an optimal current of -15.0 mA cm-2 at 0 V. Joint characterizations of X-ray photoelectron and X-ray absorption spectroscopies demonstrated that the phosphate material dominantly coordinated with the WS2 component in PO-MoWS. Moreover, this phosphate material induced a large number of sulfur vacancies in the PO-MoWS/Si electrodes that contributed to the ideal catalytic activity. Herein, TiO2 thin films were prepared as the protective layer to improve the stability of photocathodes. The PO-MoWS/2 nm TiO2/Si electrode maintained 83.8% of the initial photocurrent after chronoamperometric measurement was performed for 8000 s.

New Oxindole-Bridged Acceptors for Organic Sensitizers: Substitution and Performance Studies in Dye-Sensitized Solar Cells.

New D-π-A configured organic sensitizers featuring halogen-substituted oxindole-bridged acceptor units have been synthesized for dye-sensitized solar cells applications. Among fluorine, bromine, and iodine substitution, the cell based on bromine incorporated dye exhibited the highest efficiency. The oxindoles in these sensitizers were found to assist the electron injection through the chelation of their amide carbonyl groups to the TiO2 surface. This study provides an alternate approach for future rational dye design to gain excellent DSSC performance.

Alcohol-Guided Growth of Two-Dimensional Narrow-Band Red-Emitting K2TiF6:Mn4+ for White-Light-Emitting Diodes.

The use of red phosphors with low light-scattering loss could improve the luminous efficacy and color rendering of white-light-emitting diodes (LEDs). Thus, the discovery of such phosphors is highly desired. In this work, high-efficiency two-dimensional red-emitting K2TiF6:Mn4+ (KTFM) were synthesized via an alcohol-assisted coprecipitation route. The synergistic effects of 1-propanol and hydrofluoric acid on the growth of KTFM microsheets (MSs) were studied through the first-principles calculations, which revealed that 1-propanol promoted the growth of KTFM MSs by preferentially adsorbing on the H-terminated K2TiF6 (001) surface. The photoluminescence quantum efficiency (QE) of Mn4+-activated K2TiF6 MSs was highly related to their size and thickness. The morphology-optimal KTFM MSs presented high internal QE (>90%), external QE (>71%), and thermal quenching temperature (102% at 150 °C relative to that at 25 °C). A prototype phosphor-converted LED with KTFM as the red-emitting component showed excellent color rendition ( Ra = 91, R9 = 79) and high luminous efficacy (LE = 156 lm/w).

Novel Fluorescence Sensor Based on All-Inorganic Perovskite Quantum Dots Coated with Molecularly Imprinted Polymers for Highly Selective and Sensitive Detection of Omethoate.

All-inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I) have attracted considerable attention with superior electrical and photophysical properties. In this study, luminescent perovskite (CsPbBr3) quantum dots (QDs) as sensing elements combined with molecularly imprinted polymers (MIPs) are used for the detection of omethoate (OMT). The new MIPs@CsPbBr3 QDs were synthesized successfully through the imprinting technology with a sol-gel reaction. The fluorescence (FL) of the MIPs@CsPbBr3 QDs was quenched obviously on loading the MIPs with OMT, the linear range of OMT was from 50 to 400 ng/mL, and the detection limit was 18.8 ng/mL. The imprinting factor was 3.2, which indicated excellent specificity of the MIPs for the inorganic metal halide (IMH) perovskites. The novel composite possesses the outstanding FL capability of CsPbBr3 QDs and the high selectivity of molecular imprinting technology, which can convert the specific interactions between template and the imprinted cavities to apparent changes in the FL intensity. Hence, a selective and simple FL sensor for direct and fast detection of organophosphorus pesticide in vegetable and soil samples was developed here. The present work also illustrates the potential of IMH perovskites for sensor applications in biological and environmental detection.

Integrated Surface Modification to Enhance the Luminescence Properties of K2TiF6:Mn4+ Phosphor and Its Application in White-Light-Emitting Diodes.

Narrow-band Mn4+-doped fluoride phosphors have become a research hotspot worldwide. In this study, we propose integrated surface modification processes to enhance the performance and stability of the luminescence properties of K2TiF6:Mn4+ (KTF) phosphor. These integrated process are applied in the initial synthesis step, coating of the as-synthesized powder post-treatment process, and during the application of the phosphor in the white-light-emitting diode (WLED) device. Surface etching is conducted to remove impurities and small particles in KTF. Double-shell coating forms a stable protective layer outside the KTF. Atomic layer deposition is employed for the surface of the WLED device.

The effect of cis-trans configurational difference on the performance of pyridylimine-based ruthenium sensitizers.

New heteroleptic Ru(ii) complexes consisting of pyridylimine as an ancillary ligand were synthesized and characterized for applications in dye sensitized solar cells. Complexes with cis and trans configurations around the central ruthenium metal were obtained using simple synthetic protocols by varying the substituents on the pyridylimine ligands. The geometries of these complexes were confirmed by single crystal X-ray analysis. The effect of the difference in the configurations of these complexes on their device performances was studied and the sensitizer with a trans arrangement around the metal showed a higher overall conversion efficiency (η) of 7.27% than that of the cis configured complex (η = 2.04%).

Effect of Ammonium Salts on the Hydrothermal Synthesis of TiO2 Nanocubes for Dye-Sensitized Solar Cells.

TiO2 nanocubes were synthesized via hydrolysis condensation of titanium tetra-isopropoxide (TTIP) in aqueous media, followed by hydrothermal treatment with ammonium salts. Various ammonium salts with different alkyl chain such as ammonium hydroxide (NH4OH), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH) and tetrabutylammonium hydroxide (TBAH) were investigated. The crystalline phase, shape, and morphology of TiO2 nanocubes were studied by XRD, TEM, and SEM analysis. These TiO2 nanocubes were pure anatase phase and tended to assemble with well-ordered and close-packed domains. Both alkyl chain length of ammonium salts and hydrothermal duration affected the TiO2 nanocube formation process. The ammonium salts with longer alkyl chain formed TiO2 nanocubes in shorter hydrothermal time and offered the smallest particle size. The above TiO2 nanocubes were applied as photoanode materials in N719 anchored dye-sensitized solar cells and one of the cells exhibited the maximum power conversion efficiency of 7.85%.

Water-Resistant Efficient Stretchable Perovskite-Embedded Fiber Membranes for Light-Emitting Diodes.

Cesium lead halide perovskite nanocrystals (NCs) with excellent intrinsic properties have been employed universally in optoelectronic applications but undergo hydrolysis even when exposed to atmospheric moisture. In the present study, composite CsPbX3 (X = Cl, Br, and I) perovskite NCs were encapsulated with stretchable (poly(styrene-butadiene-styrene); SBS) fibers by electrospinning to prepare water-resistant hybrid membranes as multicolor optical active layers. Brightly luminescent and color-tunable hydrophobic fiber membranes (FMs) with perovskite NCs were maintained for longer than 1 h in water. A unique remote FMs packaging approach was used in high-brightness perovskite light-emitting diodes (PeLEDs) for the first time.

Effect of Extended Conjugation of N-Heterocyclic Carbene-Based Sensitizers on the Performance of Dye-Sensitized Solar Cells.

We report the synthesis, characterization, and photovoltaic properties of four ruthenium complexes (CI101, CBTR, CB111, and CB108) having various N-heterocyclic carbene ancillary ligands, pyridine-imidazole, -benzimidazole, -dithienobenzimidazole, and -phenanthroimidazole, respectively. These complexes were designed to investigate the effect of extended conjugation ordained from ring fusion on the power conversion efficiencies of the solar cells. The device sensitized by CB108, the pyridine-phenanthroimidazole conjugated complex, showed an improved efficiency (9.89%) compared to those of pyridine-benzimidazole conjugated system (CBTR, 9.72%) and the parent unfused ring system (CI101, 6.24%). Surprisingly, the sulfur-incorporated pyridine-dithienobenzimidazole system (CB111, 9.24%) exhibited a little lower efficiency than that of N719 (9.41%). The enhanced photovoltaic performance of CB108 was mainly attributed to the increase in electron lifetime and diffusion length confirmed by the electrochemical impedance spectroscopy.

Antibacterial Property and Cytotoxicity of a Poly(lactic acid)/Nanosilver-Doped Multiwall Carbon Nanotube Nanocomposite.

A novel method was used to synthesize a nanosilver-doped multiwall carbon nanotube (MWCNT-Ag), and subsequently, the novel poly(lactic acid) (PLA)- and MWCNT-Ag-based biocompatible and antimicrobial nanocomposites were prepared by melt blending. Based on energy dispersive X-ray spectrometry images, an MWCNT-Ag was successfully synthesized. The effect of the MWCNT-Ag on the PLA bionanocomposites was investigated by evaluating their thermal and mechanical properties, antifungal activity, and cytotoxicity. The nanocomposites exhibited a high degree of biocompatibility with the MWCNT-Ag content, which was less than 0.3 phr. Furthermore, tensile strength testing, thermogravimetric analysis, differential scanning calorimetry, and antibacterial evaluation revealed that the tensile strength, thermostability, glass transition temperature, and antibacterial properties were enhanced by increasing the MWCNT-Ag content. Finally, hydrolysis analysis indicated that the low MWCNT-Ag content could increase the packing density of PLA.

Carbon footprint assessment of recycling technologies for rare earth elements: A case study of recycling yttrium and europium from phosphor.

Rare earth elements are key raw materials in high-technology industries. Mining activities and manufacturing processes of such industries have caused considerable environmental impacts, such as soil erosion, vegetation destruction, and various forms of pollution. Sustaining the long-term supply of rare earth elements is difficult because of the global shortage of rare earth resources. The diminishing supply of rare earth elements has attracted considerable concern because many industrialized countries regarded such elements as important strategic resources for economic growth. This study aims to explore the carbon footprints of yttrium and europium recovery techniques from phosphor. Two extraction recovery methods, namely, acid extraction and solvent extraction, were selected for the analysis and comparison of carbon footprints. The two following functional units were used: (1) the same phosphor amounts for specific Y and Eu recovery concentrations, and (2) the same phosphor amounts for extraction. For acid extraction method, two acidic solutions (H2SO4 and HCl) were used at two different temperatures (60 and 90°C). For solvent extraction method, acid leaching was performed followed by ionic liquid extraction. Carbon footprints from acid and solvent extraction methods were estimated to be 10.1 and 10.6kgCO2eq, respectively. Comparison of the carbon emissions of the two extraction methods shows that the solvent extraction method has significantly higher extraction efficiency, even though acid extraction method has a lower carbon footprint. These results may be used to develop strategies for life cycle management of rare earth resources to realize sustainable usage.

Enhancement of Power Conversion Efficiency of TiO2-Based Dye-Sensitized Solar Cells on Various Acid Treatment.

The surface modification of the TiO2 photoelectrode film is one of the promising ways to improve the photovoltaic performance of dye-sensitized solar cell (DSSC). In this work for the acid treatment of TiO2 powder, fluorine containing compounds such as trifluoroacetic acid was carried out to enhance the properties of photoanode. In order to investigate the effect of trifluoroacetyl group, the TiO2 nanopowders were also treated with different acids such as acetic acid, nitric acid, hydrochloric acid, and sulfuric acid and their properties were compared. The TiO2 powders treated with both acetic acid and TFA have possessed smooth surface morphologies as well as enhanced particle dispersions with reduced particle sizes. Photoelectrodes prepared for these two kinds of TiO2 powders accommodated high amounts of dye loading and exhibited excellent light transmittance (wavelength region of 400­600 nm). Electrochemical impedance spectroscopy analysis showed the smallest radius of the semicircle which indicates the enhanced rate of electron transport for the cell based photoelectrode with trifluoroacetic acid treated TiO2 powder. The solar cell from the untreated TiO2 film showed the power conversion efficiency of 8.86% and the highest efficiency of 9.51% was achieved by the cell fabricated from trifluoroacetic acid treated TiO2 film.

Organic Photosensitizers Incorporating Rigidified Dithieno[3,2-f:2',3'-h]quinoxaline Segment Tethered with Thiophene Substitutes for Dye-Sensitized Solar Cells.

Metal-free D-π-RS-π-A type sensitizers, consisting of triphenylamine as the electron donor, 2,3-bis(3-(2-ethylhexyl)-5-methylthiophen-2-yl)dithieno[3,2-f:2',3'-h]quinoxaline (DTQT) as the rigidified conjugation spacer (RS), thiophene as the π-spacer, and 2-cyanoacrylic acid as the acceptor/anchor, have broad absorption spectra ranging from 350 to 550 nm and a high molar extinction coefficient up to >46 200 M(-1) cm(-1). Under simulated AM 1.5 G illumination, the dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions in the range of 6.78% to 8.27%. The best efficiency is slightly higher than that of N719-based standard DSSC (7.92%). The efficiency can be further boosted to 8.51% by optimizing the concentration of LiI electrolyte.

New Pyridinium Ylide Dyes for Dye Sensitized Solar Cell Applications.

Novel organic pyridinium ylide sensitizers (NO109-111) consisting of various anchoring groups were synthesized and characterized for applications in dye sensitized solar cells. Compared with the pyridine-N-oxide dye (NO108), the ylide sensitizers with strong electron-withdrawing acceptors exhibited dominant ultraviolet absorption properties and efficient binding abilities to the TiO2 surface. Among these dyes, the pyridinium ylide NO111 sensitized solar cell showed the highest efficiency (5.15%), which was improved to 7.41% by employing coadsorbent chenodeoxycholic acid.